JP5657389B2 - Use of vulcanizable rubber mixtures for vulcanizable rubber mixtures and rubber products - Google Patents

Description

  The present invention relates to vulcanizable rubber mixtures and to their use for rubber products, particularly vehicle tires and vehicle tire treads, but belts, industrial hoses or vibration dampers and impacts on conveyor systems that may have exposure to weathering effects. It also relates to the use of vulcanizable rubber mixtures for industrial rubber products such as dampers.

  The rubber products mentioned above must actually meet various requirements. In order to adjust the properties of industrial rubber, it is common to use various modified natural and synthetic rubber polymers with the intention of optimizing specific physical and mechanical properties of vulcanized products. It is a practice. For example, rubber products, particularly vehicle tires, need to have good elasticity, low wear and good adhesion on various substrates and must maintain their properties at high and low temperatures.

  The use properties of vulcanized rubber or rubber used for vehicle tires, in particular through the selection of the rubber polymer used, through the functionalization of the rubber polymer used, and the chemical bonding and / or adsorption to the filler. It is essentially adjusted through the bond / physical bond and through the choice of fillers and additives.

  Tire rubber compounds, particularly for treads, often include olefin polymers with or without aryl side chains. A very frequently used material in tire tread mixtures is a copolymer rubber composed of conjugated dienes and aromatic vinyl compounds. SBR rubber (styrene-butadiene rubber) is the most famous member of this group.

  Along with random SBR copolymers, block copolymers are also known, and the formation of blocks appears to have a decisive influence on several use properties.

  EP 1110998 discloses diene polymers modified terminally by silanol groups and with or without polysiloxane spacers. The diene polymer can be SBR rubber. These elastomers improve the interaction with the filler, but are difficult to process.

  Accordingly, it is an object of the present invention to improve the processability of SBR-type pre-elastomers that are at least partially functionalized at the chain ends without compromising the performance and desired mechanical properties of the vulcanized product. .

  SBR type polymers as defined herein are copolymers of aromatic vinyl monomers and conjugated dienes, preferably styrene and conjugated dienes. The SBR type polymer may have a random distribution of monomers, ie a statistical distribution, an example of which is common SSBR (a copolymer of styrene and 1,3-butadiene). There are also SBR type block copolymers, in particular SBR polymers with controlled microstructure.

The object of the present invention is to add a filler, at least one filler and, where appropriate, at least one polymer that is at least functionalized at one chain end (terminally) to bind to the additive. The amount of polymer functionalized at the end in the rubber mixture reaches 10 to 100 phr and the following items:
a) the functionalized polymer can be represented by the formula F1-A-F2;
b) Alternatively, the functionalized polymer mixture is a mixture of a linear or branched or radial coupling product of F1-A-units linked by a polyvalent coupling agent and a), wherein
F1 represents the terminal functionalization of the polymer chain, preferably the following chemical groups: —OH, —COOH, —COX (X is halogen), —SH, —CSSH, —NCO, amine, epoxy, S -Represents a heterocyclic residue and an N-heterocyclic residue, preferably one of heterocycloalkanyl and heterocycloalkenyl, in particular pyrrolidinyl,
F2 represents a terminal functionalization different from F1, and A is between one or more conjugated dienes and one or more aromatic vinyl monomers in any desired cis or trans conformation. (Represents the polymer chain of the polymer formed by copolymerization)
It is solved by a vulcanizable rubber mixture characterized in that it comprises a polymer or a mixture of polymers according to the above.

As used herein, the term phr (parts by weight per 100 parts by weight of rubber) is a daily term for the amount to mix the compound in the rubber industry. The amount added in parts by weight of the individual substances is always based here on 100 parts by weight of the total weight of all the rubber present in the mixture.
The polymer introduced into the vulcanizable rubber mixture according to the invention can also be represented by the following formula in which the tetravalent coupling agent C is selected.

  Preferably C is Si or Sn. In principle, any coupling agent commonly used in polymer chemistry for the coupling of elastomers can be used.

The process for the preparation of certain polymers in rubber mixtures according to the invention is
Forming a functionalization initiator for functionalization with -F1, followed by copolymerizing a conjugated diene and an aromatic vinyl monomer;
For alternative a) adding a functionalizing agent for F2, ie adding an agent that functionalizes the copolymer still having active anionic chains;
-For alternative b), adding a coupling agent and then partially linking the active polymer chains by F2 functionalizing the remaining active chains.

  Copolymerization of SBR type copolymers is usually accomplished by a process of anionic polymerization in solution.

  As initiator, n-butyl-lithium can be used. In order to produce a functionalized initiator, as a general procedure, the functionalizing agent for F1 is first reacted with the initiator. In a preferred example, pyrrolidine is used. Because of its high reactivity, pyrrolidine reacts rapidly with n-butyl-lithium, even in the presence of monomers, to initiate a type of pyrrolidine-lithium functional initiator that initiates copolymerization in situ. (K. Morita et al., Polymer Preprints, 37 (2), page 700, 1996).

  The coupling agent having two or more functional groups is preferably represented by the following structure.

SiR _n X _m (where 0 ≦ n ≦ 2, 2 ≦ m ≦ 4, n + m = 4, X = Hal or —OR, R = H, in each case a straight chain having 1 to 20 carbon atoms or Branched alkyl, cycloalkyl, aryl, alkylaryl, aralkyl or vinyl)

SnR _n X _m (where 0 ≦ n ≦ 2, 2 ≦ m ≦ 4, n + m = 4, X = Hal or —OR, R = H, in each case a straight chain having 1-20 carbon atoms or Branched alkyl, cycloalkyl, aryl, alkylaryl, aralkyl or vinyl)

R (R ′) _m (wherein R is as above except H, R ′ is a vinyl group, m is the number of units different from 2 to 4); Divinylbenzene (DVB) can be used.

Most preferably, however, the coupling agent is silicon tetrachloride (SiCl ₄ ) or stannic tetrachloride (SnCl ₄ ).

  Preferably, the polymer chain units A contained in the vulcanizable rubber mixture according to the invention are randomly, ie statistically polymerized polymers, ie “A” is a random distribution of comonomer units, ie Have a statistical distribution.

  The diolefin can generally be a diene monomer having from 4 to about 10 carbon atoms, specific examples being 1,3-butadiene, 2-alkyl-1,3-butadiene, 2,3 -Dialkyl-1,3-butadiene, 2-alkyl-3-alkyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene and the like.

  The polyisoprene can be either 1,4-polyisoprene or 3,4-polyisoprene. The polybutadiene can be either 1,4-polybutadiene or vinyl-polybutadiene.

  Most preferably, the conjugated diene of chain A is butadiene, preferably 1,3-butadiene. Isoprene or a mixture of butadiene and / or isoprene can also be used within the scope of the present invention.

  In a preferred embodiment of the present invention, the aromatic vinyl compound is styrene. Orthomethyl styrene, metamethyl styrene and / or paramethyl styrene, vinyl toluene, pt-butyl styrene, methoxy styrene, vinyl mesitylene and / or divinyl benzene are of low commercial importance. Nevertheless, they can also be used or added.

  The main chain polymer is composed of a conjugated diene and an aromatic vinyl compound and is microsequence polymerized comprising 2 to 10 units, preferably 3 to 10 units, more preferably 3 to 6 units long comonomer microblocks. It can be a copolymer.

  The content of 1,2-vinyl units in the polymer chain A is preferably 8% to 80%, more preferably 11% to 80%, even more preferably, based on the total of conjugated dienes introduced into the copolymer Is from 10% to 70%, and it is also possible to show different contents of 1,4-cis and 1,4-trans units and 3,4-vinyl units depending on the conjugated diene used.

  The composition of polymer chain A in weight percent is preferably in the range of 5% to 50% for aromatic vinyl monomers and in the range of 50% to 95% for conjugated dienes, preferably aromatic vinyl monomers. In the range of 15% to 40% and in the range of 60% to 85% with respect to the conjugated diene.

  For the polymer of chain A, at least one of the following conditions should be met. The Mooney viscosity (ML1 + 1 at 100 ° C.) is preferably in the range of 30 to 90. The average molecular weight is in the range of Mw = 80,000 to 700,000 based on polystyrene standards, and the polydispersity is in the range of 1.05 to 4.0. The glass transition temperature Tg is in the range of -92 ° C to -1 ° C.

  Advantageously, the mixture comprises 30 to 90 phr of elastomer according to a) or b) and a residual rubber content of 10 to 70 phr is preferably natural rubber (NR), synthetic polyisoprene (IR), polybutadiene (BR) or It is composed of at least one elastomer rubber from the group of polychloroprene (CR), styrene butadiene (SBR), isoprene butadiene (IBR) or styrene isoprene butadiene (SIBR).

a) That is, the ratio of linear polymer according to F1-A-F2 to astral coupling product or radiator coupling product (F1-A) _n C, where n corresponds to the number of bonds in C Most advantageously, it is in the range of 90:10 to 10:90, preferably 80:20 to 50:50, more preferably 80:20 to 60:40.

The functional groups and preferably the chain end groups F2 are preferably the following list; degree of functionalization based on the weight of the elastomer: 30% to 100%, preferably 50 to 95%, particularly preferably 75% to 95%;
Silyl, silanol, or polysiloxane groups bonded to the polymer chain with or without spacers in each case, and siloxane groups containing amino groups and siloxane groups containing polysiloxane groups, and preferably the structure: -SiH ₂ (OH), —Si (R ₁ ) ₂ (OH), —SiH (OH) ₂ , —SiR ₁ (OH) ₂ , —Si (OH) ₃ , —Si (OR ₁ ) ₃ , — (SiR ₁₎ R ₂ O) _x -R ₃ , -Si (R ₃ ) _3-m (X) _m (wherein X is halogen, x is the number of repeating units, 1 to 500, and m is linked) The number of groups, 0 to 3, R ₁ and R ₂ are the same or different, in each case preferably 1-20 carbon atoms, preferably straight-chain or branched alkoxy or alkyl, cycloalkyl, aryl , An alkylaryl, aralkyl or vinyl group, wherein R ₃ is H, or a linear or branched alkyl having 1-20 carbon atoms or a mononuclear aryl group, and the formula -A1-Si- (A2-N ((H _k / R ₁ ) _2-k) )) _y (OR ₁ ) _z (R ₃ ) _{3- (y + z)} (wherein R ₁ and R ₂ are the same or different, and in each case 1 to K can vary from 0 to 2 provided that it can be a straight or branched alkyl, cycloalkyl, aryl, alkylaryl, aralkyl or vinyl group having 20 carbon atoms and a mononuclear aryl group. , Y can vary from 1 to 3, z can vary from 0 to 2, 0 ≦ y + z ≦ 3, R ₃ is H, or 1-20 in each case of Linear or branched alkyl having a primary atom or a mononuclear aryl group, wherein A1 and A2 are chains of up to 12 carbon atoms, linear or branched, preferably alkyl, allyl or vinyl). A functional group selected from the above silyl, silanol or siloxane groups, preferably represented by:

  Functionalized F2 can usually be introduced via a functionalization terminator. Alternatively, once the polymerization is stopped, the active polymer chain end can be reacted with a compound containing the desired functional group to be added to the end and also includes a suitable leaving group. By way of example, this is reactive with compounds such as ethylene oxide, benzophenone, carbon dioxide, dialkylaminobenzaldehyde, carbon disulfide, alkoxysilane, alkylphenoxysilane, phenoxysilane, etc. as previously known from the prior art to those skilled in the art. It can be achieved via reaction with polymer ends. By way of example, EP 396,780 or EP 849,333 lists suitable processes and groups.

In a preferred embodiment, F2 is of the general formula-[-Si (alkyl) _2- O-] _x- , where x is in the range of 1 to 500 units per chain, followed by a silanol terminated-[ --Si (alkyl) _2- OH] followed by a polysiloxane group. In the most preferred embodiment, alkyl is methyl. Therefore, F2 can be introduced by hexamethylcyclotrisiloxane (D ₃ ) as a chain terminator.

According to it, a highly preferred embodiment of the polymer according to a) is “Amine-A- (SiR ₁ R ₂ —O—) _x SiR ₁ R ₂ OH, wherein R ₁ , R ₂ = alkyl and x = 1-500) The amine groups are of the formula -N (R ₁ ) ₂ , -N (R ₂ ) ₂ , -N (R ₁ R ₂ ), -N (R ₁ ) H, -N (R ₂ ) H, —NH ₂ , wherein R ₁ and R ₂ = in each case a linear or branched alkyl, cycloalkyl, aryl, alkaryl, aralkyl or vinyl group having 1 to 20 carbon atoms Advantageously, A is S-SSBR and R ₁ = R ₂ = CH _3. A highly preferred embodiment of a branched or astral coupling product is (amine _-A-) in n C (wherein, same as above Eye and C = a Sn or Si).

  Polysiloxane sequences or polysiloxane blocks can also be introduced and distributed along the polymer chain. However, the polysiloxane sequence or polysiloxane block is optionally terminal.

  Functionalization, F1 and F2, to improve the adhesion or bond strength between rubber and filler, ie carbon black filler or silicon oxide (preferably generally white in this case) filler be introduced.

  The mixture comprises plasticizers, antioxidants, UV stabilizers, mold release agents, vulcanization accelerators and retardants, activators such as zinc oxide and fatty acids (eg stearic acid), conventional parts by weight of wax. And conventional additives such as kneading aids. Bifunctional coupling agents, particularly preferably silanes and amines, can also be used as additives for the rubber mixture.

  The filler present in the mixture can preferably be what is known as a “white filler” or carbon black. In a preferred embodiment, the filler comprises at least one silicon oxide-based filler (silica, silicic acid), or comprises a separate “white” filler individually or in the mixture, and in the mixture Carbon black can also be included.

  The filler preferably comprises a mixture composed of at least one silicon oxide based filler and at least one carbon black grade. Silicone fillers and carbon blacks suitable for industrial rubber moldings and tire mixtures are known in the prior art and can be used herein. The fillers and rubbers of the mixture can likewise be modified in a manner known in principle from the prior art relating to rubber mixtures.

The white filler can more preferably be an oxidised and / or hydrated inorganic filler or mineral filler, or can comprise any desired combination of these materials. The white filler is preferably selected from the group of silica (SiO ₂ ), phyllosilicate, chalk, starch, and oxides and / or hydroxides of aluminum, magnesium, titanium or zinc.

  The proportion of filler present in the mixture is advantageously 20 to 200 phr, preferably 30 to 150 phr, more preferably 30 to 130 phr.

  The invention relates to a rubber product, in particular a vehicle tire, preferably a vehicle tire tread, a hose, a belt, an industrial molding, a vibration damper or an impact damper or wire coating and a rubber according to the invention as described above for the production of the product itself. It also encompasses the use of mixtures. All these products benefit from the improved properties of the rubber elastomer according to the invention, in particular the improved processability before vulcanization.

  The invention will now be described in more detail in connection with the following examples and tests. The examples and tests are given for easier understanding of the invention only, ie for illustrative purposes only, and are not intended to define the scope of the invention in any way.

  The polymers mentioned in the following examples are shown as follows.

  The improved processability is evident at the lower viscosity before vulcanization of the rubber mixture according to the invention, exemplified by the value of the minimum torque. Accordingly, embodiments according to the present invention exhibit desirable properties for the purposes of the present invention.

When testing specimens, the following test methods were used.
-Shore A hardness at room temperature and 70 ° C for DIN 53505-Rebound resilience at room temperature and 70 ° C for DIN 53512-Tensile strength at room temperature for DIN 53504-Elongation at break (tear elongation) at room temperature for DIN 53504
-Stress values at 100% static elongation and 300% static elongation at room temperature for DIN 53504-Minimum torque according to DIN 53523
In addition, although this application is related with the invention as described in a claim, the following may also be included as another aspect.
1. A vulcanizable rubber mixture comprising a filler, at least one filler and, where appropriate, at least one polymer functionalized at least at one chain end (terminally) to bind to the additive. The amount of terminally functionalized polymer in the rubber mixture reaches 10 to 100 phr and the following items:
a) the functionalized polymer can be represented by the formula F1-A-F2;
b) Alternatively, the mixture of functionalized polymers is a mixture of a) with a multivalent coupling agent, preferably an F1-A-unit astral coupling product or radial coupling product linked by Sn or Si and a). Wherein F1 represents terminal functionalization of the polymer chain, preferably the following chemical groups: —OH, —COOH, —COX (X is halogen), —SH, —CSSH, —NCO , Amine, epoxy, S-heterocyclic residue and N-heterocyclic residue, preferably one of heterocycloalkanyl and heterocycloalkenyl, especially pyrrolidinyl, wherein F2 is a terminal function different from F1 And A represents a polymer formed by copolymerization between one or more conjugated dienes and one or more aromatic vinyl monomers. Represents an Rimmer chain)
A vulcanizable rubber mixture, characterized in that it comprises a polymer or a mixture of polymers according to 1.
2. 2. The vulcanizable rubber mixture according to 1 above, wherein A is a polymer polymerized randomly or statistically.
3. 3. The vulcanizable rubber mixture according to 1 or 2 above, wherein the conjugated diene of chain A is butadiene, preferably 1,3-butadiene or isoprene or a mixture of butadiene and / or isoprene.
4). The above 1-3, wherein the aromatic vinyl compound is styrene, orthomethyl styrene, metamethyl styrene and / or paramethyl styrene, vinyl toluene, pt-butyl styrene, methoxy styrene, vinyl mesitylene and / or divinyl benzene. The vulcanizable rubber mixture according to any one of the above.
5. A main chain polymer, which is a microsequence polymerized copolymer composed of a conjugated diene and an aromatic vinyl compound, is a micromonomer of a comonomer having a length of 2 to 10 units, preferably 3 to 10 units, more preferably 3 to 6 units. The vulcanizable rubber mixture according to any one of the above 1 to 4, which comprises a block.
6). The content of 1,2-vinyl units in the polymer chain A is 8% to 80%, preferably 11% to 80%, more preferably 10%, based on the total of conjugated dienes introduced in the copolymer Any of the above 1 to 5 characterized in that it can show different contents of 1,4-cis and 1,4-trans units and 3,4-vinyl depending on the conjugated diene used A vulcanizable rubber mixture according to claim 1.
7). The composition of polymer chain A in weight percent is in the range of 5% to 50% for aromatic vinyl monomers, in the range of 50% to 95% for conjugated dienes, preferably 15% for aromatic vinyl monomers The vulcanizable rubber mixture according to any one of the above 1 to 6, characterized in that it is in the range of -40% and in the range of 60% to 85% with respect to the conjugated diene.
8). The following conditions for the polymer of chain A: Mooney viscosity (ML1 + 4 at 100 ° C.); in the range of 30-90, average molecular weight based on polystyrene standards; in the range of Mw = 80,000-700,000, polydispersity; 1 The additive according to any one of 1 to 7 above, which satisfies at least one of the following: 0.05 to 4.0, glass transition temperature Tg; -92 ° C to -1 ° C. Sulfur rubber mixture.
9. Said mixture comprises an elastomer 30-90 phr according to a) or b) and a residual rubber content 10-70 phr is preferably natural rubber (NR), synthetic polyisoprene (IR), polybutadiene (BR) or polychloroprene (CR). The vulcanizable rubber mixture according to any one of the above 1 to 8, which is composed of at least one elastomer rubber from the group of SBR, SBR, IBR or SIBR.
10. F2 is the following list; degree of functionalization based on the weight of the elastomer: 30% to 100%, preferably 50 to 95%, particularly preferably 75% to 95%; in each case with or without a spacer Silyl, silanol, or polysiloxane groups bonded to siloxane groups, and siloxane groups containing amino groups and siloxane groups containing polysiloxane groups, and preferably the structures: —SiH ₂ (OH), —Si (R ₁ ) ₂ ( _{OH), - SiH (OH)} 2, -SiR 1 (OH) 2, -Si (OH) 3, -Si (OR 1) 3, - (SiR 1 R 2 O) x -R 3, -Si (R ₃ ) _3-m (X) _m (wherein X is halogen, x is the number of repeating units, 1 to 500, m is the number of linking groups, 0 to 3; R ₁ and R ₂ are the same Or in each case preferably a straight-chain or branched alkoxy or alkyl, cycloalkyl, aryl, alkylaryl, aralkyl or vinyl group having 1 to 20 carbon atoms, R ₃ is H or 1 to straight or branched alkyl having 20 carbon atoms or mononuclear aryl group, and the formula _{-Al-Si- (A2-N (} (H k / R 1) 2-k))) y (oR 1) z (R ₃ ) _{3- (y + z) wherein} R ₁ and R ₂ are the same or different and in each case 1-20 carbon atoms and a mononuclear aryl group, a straight-chain or branched alkyl, cycloalkyl , K can vary from 0 to 2 and y is 1 provided that it can be an aryl, alkylaryl, aralkyl or vinyl group 3 can be different, z can be different from 0 to 2, 0 ≦ y + z ≦ 3, R ₃ is H or in each case 1-20 carbon atoms or a mononuclear aryl group. A linear or branched alkyl having A1 and A2 are siloxane groups containing amine groups represented by a chain of up to 12 carbon atoms, linear or branched, preferably alkyl, allyl or vinyl) 10. The vulcanizable rubber mixture according to any one of the above 1 to 9, wherein the vulcanizable rubber mixture is a functional group selected from the silyl, silanol or siloxane groups preferably represented by
11. Filler is preferably silica (SiO ₂ ), phyllosilicate, chalk; oxidized and / or hydroxylated inorganic filler or mineral selected from the group of oxides and / or hydroxides of aluminum, magnesium, titanium or zinc 11. The vulcanizable rubber mixture according to any one of the above 1 to 10, which consists entirely or mainly of a filler.
12 The vulcanizable rubber mixture as described in 11 above, wherein the proportion of the filler in the mixture is 20 to 200 phr, preferably 30 to 150 phr, more preferably 30 to 130 phr.
13. Use of a rubber mixture according to any one of claims 1 to 12 for the production of rubber products, in particular vehicle tires, preferably vehicle tire treads, hoses, belts, industrial moldings or vibration dampers or impact dampers.
14 An industrial rubber product comprising the vulcanized rubber mixture according to any one of 1 to 13 above.
15. 15. The industrial rubber product as described in 14 above, wherein the product is a tread for a vehicle tire.
16. 16. A vehicle tire having the tread described in 15.

Claims (16)

Vulcanizable rubber comprising at least one polymer functionalized at the end of the chain (terminally) for bonding to the filler and at least one filler and with or without additives The amount of the polymer functionalized at the end in the rubber mixture reaches 10-100 phr and the following items:
a) the functionalized polymer can be represented by the formula F1-A-F2;
b) Alternatively, the mixture of functionalized polymers is a mixture of a) with astral or radial coupling products of F1-A-units linked by Sn or Si, where F1 is Represents terminal functionalization of the polymer chain and represents an N-heterocyclic residue, F2 is of the general formula [Si (alkyl) _2- O-] _x , where x is 1 to 500 units per chain Represents a polysiloxane group followed by a silanol terminated [Si (alkyl) _2- OH] , and A represents between one or more conjugated dienes and one or more aromatic vinyl monomers. Represents the polymer chain of a polymer formed by copolymerization of
Look containing a polymer or mixture of polymers according to and said additive, a plasticizer, antioxidants, UV stabilizers, mold release agents, vulcanization accelerators, vulcanization retarder, activator, waxes, kneading aid and A vulcanizable rubber mixture characterized by being selected from the group consisting of bifunctional coupling agents .   The vulcanizable rubber mixture according to claim 1, wherein A is a polymer polymerized randomly or statistically.   The vulcanizable rubber mixture according to claim 1 or 2, wherein the conjugated diene of chain A is butadiene or isoprene, or a mixture of butadiene and / or isoprene.   The aromatic vinyl compound is styrene, orthomethyl styrene, metamethyl styrene and / or paramethyl styrene, vinyl toluene, pt-butyl styrene, methoxy styrene, vinyl mesitylene and / or divinyl benzene. The vulcanizable rubber mixture according to any one of the above.   5. The main chain polymer, which is a microsequence polymerized copolymer composed of a conjugated diene and an aromatic vinyl compound, contains a comonomer microblock with a length of 2 to 10 units. A vulcanizable rubber mixture according to claim 1.   The content of 1,2-vinyl units in the polymer chain A is 8% to 80%, based on the total of conjugated dienes introduced in the copolymer, depending on the conjugated diene used, Vulcanizable rubber mixture according to any one of the preceding claims, characterized in that it can also show different contents of cis and 1,4-trans units and 3,4-vinyl.   The composition of polymer chain A in weight percent is in the range of 5% to 50% for aromatic vinyl monomers and in the range of 50% to 95% for conjugated dienes. The vulcanizable rubber mixture according to any one of the above.   The following conditions for the polymer of chain A: Mooney viscosity (ML1 + 4 at 100 ° C.); in the range of 30-90, average molecular weight based on polystyrene standards; in the range of Mw = 80,000-700,000, polydispersity; 1 It satisfies at least one of the range of 0.05 to 4.0 and the glass transition temperature Tg; the range of −92 ° C. to −1 ° C. 8. Vulcanizable rubber mixture.   A vulcanizable rubber mixture according to any one of the preceding claims, wherein the mixture comprises 30 to 90 phr of polymer according to a) or b).   The vulcanizable rubber mixture according to any one of claims 1 to 9, characterized in that the degree of functionalization of F2 based on the weight of the polymer is 30% to 100%.   11. Vulcanizable rubber mixture according to any one of the preceding claims, characterized in that the filler consists entirely or predominantly of oxidized and / or hydroxylated inorganic fillers or mineral fillers.   The vulcanizable rubber mixture according to claim 11, wherein the ratio of the filler in the mixture is 20 to 200 phr. Use of the vulcanizable rubber mixture according to any one of claims 1 to 12 for the production of rubber products.   An industrial rubber product comprising the vulcanized rubber mixture according to any one of claims 1 to 13.   The industrial rubber product according to claim 14, wherein the product is a tread for a vehicle tire.   A vehicle tire having the tread according to claim 15.